JP4711158B2 - Low temperature fired ceramic circuit board - Google Patents

Low temperature fired ceramic circuit board Download PDF

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Publication number
JP4711158B2
JP4711158B2 JP2001204522A JP2001204522A JP4711158B2 JP 4711158 B2 JP4711158 B2 JP 4711158B2 JP 2001204522 A JP2001204522 A JP 2001204522A JP 2001204522 A JP2001204522 A JP 2001204522A JP 4711158 B2 JP4711158 B2 JP 4711158B2
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low
thick film
fired ceramic
film resistor
temperature fired
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JP2003023233A (en
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昌志 深谷
俊博 中居
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Murata Manufacturing Co Ltd
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Murata Manufacturing Co Ltd
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【０００１】
【発明の属する技術分野】
本発明は、Ａｇ−Ｐｄ導体とガラスとの混合物を主成分とする厚膜抵抗体が形成された低温焼成セラミック回路基板に関するものである。
【０００２】
【従来の技術】
８００〜１０００℃で焼成する低温焼成セラミック回路基板は、セラミックと同時焼成する配線導体として、電気的特性に優れたＡｇ系導体等の低融点金属を使用できると共に、アルミナ基板と比較して誘電率が低く、信号処理の高速化に対応できる等の利点がある。この低温焼成セラミック回路基板に厚膜抵抗体を形成する場合は、ＲｕＯ2 系の厚膜抵抗体ペーストを用いることが多いが、温度変化の影響を受けにくい安定した抵抗特性が要求される回路では、厚膜抵抗体の抵抗温度係数（ＴＣＲ）を例えば±１００ｐｐｍ／℃以内にすることが要求される場合がある。
【０００３】
シート抵抗値が５０〜３００ｍΩ／□の厚膜抵抗体を形成する場合、ＲｕＯ2 系の厚膜抵抗体では上記の要求を満たすことができないため、Ａｇ−Ｐｄ導体とガラスとの混合物からなる抵抗体材料を用いて抵抗温度係数の小さい厚膜抵抗体を形成するようにしている。
【０００４】
一般に、Ａｇ−Ｐｄ導体の抵抗温度係数は、Ａｇ又はＰｄを単独で用いる場合よりも小さくなり、ＡｇとＰｄの配合比が、Ａｇ：Ｐｄ＝５０：５０の付近で抵抗温度係数が最も小さくなる。この特性から、Ａｇ−Ｐｄ導体を主導電体成分とする厚膜抵抗体は、Ａｇ：Ｐｄ＝５０：５０の付近で用いられる場合が多い。
【０００５】
【発明が解決しようとする課題】
ところが、低温焼成セラミック回路基板に形成する電極導体（厚膜配線導体）は、電気的特性を良くするために、Ａｇ導体、又は、１０重量％以下のＰｄを含むＡｇ−Ｐｄ導体により形成する場合が多い。このような電極導体上にＡｇ−Ｐｄ系の厚膜抵抗体を印刷して焼成すると、電極導体と厚膜抵抗体とのＰｄ含有量が大きく異なるため、焼成時に電極導体中のＡｇ原子がＡｇ含有量の少ない厚膜抵抗体中に拡散して、電極導体内部がポーラス化（多孔質化）する現象が発生する。その結果、電極導体と低温焼成セラミック基板との接合強度が弱くなって、信頼性が悪くなるという欠点がある。
【０００６】
この対策として、電極導体と厚膜抵抗体との間に、Ａｇ拡散防止のための中間導体層として、両者の中間的な２０〜３０重量％のＰｄを含むＡｇ−Ｐｄ導体層を形成したり、或は、電極導体（厚膜配線導体）にガラス成分を多く配合して、電極導体とセラミック基板との接合強度を大きくするようにしていた。
【０００７】
しかし、電極導体と厚膜抵抗体との間に、Ａｇ−Ｐｄの中間導体層を形成する場合は、印刷工程が増加すると共に、２０〜３０重量％のＰｄを含むＡｇ−Ｐｄ導体が新たに必要となり、コストアップするという欠点がある。また、電極導体（厚膜配線導体）のガラス含有量を多くすると、電極導体（厚膜配線導体）の導通抵抗が大きくなり、回路の電気的特性が悪くなってしまうという欠点がある。
【０００８】
本発明はこのような事情を考慮してなされたものであり、従ってその目的は、Ａｇ−Ｐｄ系の厚膜抵抗体を接続する電極導体（厚膜配線導体）と低温焼成セラミック基板との接合強度を向上して信頼性を確保しながら、コスト低減と電気的特性向上の要求も満たすことができる低温焼成セラミック回路基板を提供することにある。
【０００９】
【課題を解決するための手段】
上記目的を達成するために、上記目的を達成するために、本発明の請求項１の低温焼成セラミック回路基板は、低温焼成セラミック基板の表面に形成された電極導体と、この電極導体に接合するように形成された厚膜抵抗体とを備えたものにおいて、前記電極導体を、Ａｇ導体又はＰｄ含有量が１０重量％以下のＡｇ−Ｐｄ導体により形成し、前記厚膜抵抗体をＡｇ−Ｐｄ導体とガラスとの混合物に前記低温焼成セラミック基板を形成する低温焼結セラミック材料と主成分が同一の低温焼成セラミック材料を５重量％以上添加した抵抗体材料により形成したものである。
【００１０】
このように、低温焼成セラミック基板と同種の低温焼成セラミック材料を５重量％以上添加した抵抗体材料を用いて厚膜抵抗体を形成すれば、焼成時に厚膜抵抗体から電極導体側に低温焼成セラミック材料が拡散し、厚膜抵抗体と電極導体との間に低温焼成セラミック材料の中間層が形成される。この中間層が電極導体から厚膜抵抗体へのＡｇ拡散を防止する役割を果たし、Ａｇ拡散による電極導体内部のポーラス化が防止され、電極導体と低温焼成セラミック基板との接合強度の低下が防止される。
【００１１】
しかも、厚膜抵抗体には、低温焼成セラミック基板と同種の低温焼成セラミック材料が５重量％以上添加されているので、厚膜抵抗体と低温焼成セラミック基板との熱膨張係数の差が小さくなり、厚膜抵抗体と低温焼成セラミック基板との接合部に作用する熱応力が小さくなる。しかも、焼成時に低温焼成セラミック基板から厚膜抵抗体側にしみ出したガラス成分と厚膜抵抗体のガラス成分とが同種であるため、両方のガラス成分が融合して、厚膜抵抗体と低温焼成セラミック基板との接合強度が増加する。また、焼成時に低温焼成セラミック基板の表面にしみ出したガラス成分が電極導体（厚膜配線導体）を接着する接着剤の役割を果たし、電極導体（厚膜配線導体）の接合強度も確保される。
【００１２】
この場合、Ａｇ−Ｐｄ系の厚膜抵抗体は、ＡｇとＰｄの配合比が、Ａｇ：Ｐｄ＝５０：５０の付近で抵抗温度係数が最小になる特性があることから、請求項２のように、厚膜抵抗体の全導体の合計含有量に対するＰｄ含有量を４０重量％以上にすると良い。このようにすれば、厚膜抵抗体の抵抗温度係数を最小値に近付けることができ、温度変化の影響を受けにくい安定した抵抗特性を実現することができる。尚、厚膜抵抗体のＰｄ含有量が多くなって、電極導体と厚膜抵抗体とのＰｄ含有量の差が大きくなっても、前述したように、焼成時に厚膜抵抗体から電極導体側に低温焼成セラミック材料が拡散して、厚膜抵抗体と電極導体との間に低温焼成セラミック材料の中間層が形成されるため、この中間層によって電極導体から厚膜抵抗体へのＡｇ拡散が防止され、Ａｇ拡散による電極導体と低温焼成セラミック基板との接合強度の低下が防止される。
【００１３】
また、請求項３のように、低温焼成セラミック材料は、ＣａＯ−ＳｉＯ2 −Ａｌ2 Ｏ3 −Ｂ2 Ｏ3 系ガラス粉末とＡｌ2 Ｏ3 粉末との混合物を用いるようにしても良い。この低温焼成セラミック材料は、低誘電率、低熱膨張係数の特長があり、信号処理の高速化に対応した高性能のセラミック回路基板を形成できると共に、該低温焼成セラミック材料を厚膜抵抗体に５重量％以上添加しても、厚膜抵抗体の抵抗温度係数が増加せず、温度変化の影響を受けにくい安定した抵抗特性を得ることができる。
【００１４】
【発明の実施の形態】
以下、本発明の一実施形態を図１に基づいて説明する。低温焼成セラミック基板１１は、８００〜１０００℃で焼成した低温焼成セラミック材料で形成され、複数枚の低温焼成セラミックのグリーンシートを積層して焼成した多層基板又は単層基板のいずれであっても良い。この低温焼成セラミック基板１１を形成する低温焼成セラミック材料としては、例えばＣａＯ−ＳｉＯ2 −Ａｌ2 Ｏ3 −Ｂ2 Ｏ3 系ガラス粉末：５０〜６５重量％（好ましくは６０重量％）とＡｌ2 Ｏ3 粉末：５０〜３５重量％（好ましくは４０重量％）との混合物を用いると良い。この他、例えば、ＭｇＯ−ＳｉＯ2 −Ａｌ2 Ｏ3 −Ｂ2 Ｏ3 系ガラス粉末とＡｌ2 Ｏ3 粉末との混合物、ＳｉＯ2 −Ｂ2 Ｏ3 系ガラス粉末とＡｌ2 Ｏ3 粉末との混合物、ＰｂＯ−ＳｉＯ2 −Ｂ2 Ｏ3 系ガラス粉末とＡｌ2 Ｏ3 粉末との混合物、コージェライト系結晶化ガラス等の８００〜１０００℃で焼成できる低温焼成セラミック材料を用いても良い。
【００１５】
低温焼成セラミック基板１１の表面（又は裏面）には、Ａｇ導体又はＰｄ含有量が１０重量％以下のＡｇ−Ｐｄ導体のペーストを用いて、表層配線導体１２と電極導体１３が印刷・焼成されている。この表層配線導体１２と電極導体１３は、低温焼成セラミック基板１１と同時焼成しても良く、或は、低温焼成セラミック基板１１の焼成後に後付けで表層配線導体１２と電極導体１３を印刷・焼成しても良い。
【００１６】
ここで、表層配線導体１２や電極導体１３をＡｇ−Ｐｄ導体で形成する場合、ＰｄはＡｇのマイグレーションを抑制する役割を果たすが、Ｐｄ含有量が１０重量％よりも多くなると、半田付け性が悪くなったり、導通抵抗値が大きくなるため、Ｐｄ含有量が１０重量％以下（Ａｇ含有量が９０重量％以上）とすることが望ましい。
【００１７】
また、低温焼成セラミック基板１１の表面（又は裏面）には、一対の電極導体１３間に跨がって厚膜抵抗体１４が印刷・焼成されている。この厚膜抵抗体１４は、Ａｇ−Ｐｄ導体とガラスとの混合物に低温焼成セラミック基板１１を形成する低温焼結セラミック材料と主成分が同一の低温焼成セラミック材料を５重量％以上添加した抵抗体材料のペーストにより形成されている。更に、この厚膜抵抗体１４は、全導体の合計含有量に対するＰｄ含有量が４０重量％以上に設定されている。この厚膜抵抗体１４は、ＡｇとＰｄの配合比が、Ａｇ：Ｐｄ＝５０：５０の付近で抵抗温度係数が最小になる特性があることから、厚膜抵抗体１４のＰｄ含有量を４０〜６０重量％にすれば、厚膜抵抗体１４の抵抗温度係数が最小値近付の値となり、温度変化の影響を受けにくい安定した抵抗特性が得られる。
【００１８】
この厚膜抵抗体１４は、表層配線導体１２や電極導体１３と同時焼成したり、或は、表層配線導体１２や電極導体１３の焼成後に、厚膜抵抗体１４を印刷・焼成しても良い。
【００１９】
例えば、低温焼成セラミック基板１１を形成する低温焼成セラミック材料が、ＣａＯ−ＳｉＯ2 −Ａｌ2 Ｏ3 −Ｂ2 Ｏ3 系ガラス粉末とＡｌ2 Ｏ3 粉末との混合物により形成されている場合には、厚膜抵抗体１４には、ＣａＯ−ＳｉＯ2 −Ａｌ2 Ｏ3 −Ｂ2 Ｏ3 系ガラス粉末とＡｌ2 Ｏ3 粉末との混合物を５重量％以上添加すると良い。この際、低温焼成セラミック基板１１と厚膜抵抗体１４とで、全く同一の組成・配合比の低温焼成セラミック材料を用いることが望ましいが、低温焼成セラミック基板１１と厚膜抵抗体１４とで、ガラス粉末とＡｌ2 Ｏ3 粉末との配合比が少し異なる低温焼成セラミック材料を用いても良いことは言うまでもない。低温焼成セラミック材料のガラス粉末とＡｌ2 Ｏ3 粉末との配合比が少しぐらい異なっても、同じ組成のガラス粉末とＡｌ2 Ｏ3 粉末が配合されていれば、低温焼成セラミック材料の性質がほぼ同じになるためである。また、低温焼成セラミック基板１１と厚膜抵抗体１４とで、低温焼成セラミック材料のガラス成分の主成分が同じであれば、そのガラス成分の添加物等が若干異なっていても良い。
【００２０】
以上説明した本実施形態の構成では、低温焼成セラミック基板１１以上説明した本実施形態の構成では、低温焼成セラミック基板１１を形成する低温焼結セラミック材料と主成分が同一の低温焼成セラミック材料を５重量％以上添加した抵抗体材料を用いて厚膜抵抗体１４を形成したので、焼成時に厚膜抵抗体１４から電極導体１３側に低温焼成セラミック材料が拡散し、厚膜抵抗体１４と電極導体１３との間に低温焼成セラミック材料の中間層が形成される。この中間層が電極導体１３から厚膜抵抗体１４へのＡｇ拡散を防止する役割を果たし、Ａｇ拡散による電極導体１３内部のポーラス化が防止され、電極導体１２と低温焼成セラミック基板１１との接合強度の低下が防止される。
【００２１】
しかも、厚膜抵抗体１４には、低温焼成セラミック基板１１を形成する低温焼結セラミック材料と主成分が同一の低温焼成セラミック材料が５重量％以上添加されているので、厚膜抵抗体１４と低温焼成セラミック基板１１との熱膨張係数の差が小さくなり、厚膜抵抗体１４と低温焼成セラミック基板１１との接合部に作用する熱応力が小さくなる。しかも、焼成時に低温焼成セラミック基板１１から厚膜抵抗体１４側にしみ出したガラス成分と厚膜抵抗体１４のガラス成分とが同種であるため、両方のガラス成分が融合して、厚膜抵抗体１４と低温焼成セラミック基板１１との接合強度が増加する。また、焼成時に低温焼成セラミック基板１１の表面にしみ出したガラス成分が電極導体１３（表層配線導体１２）を接着する接着剤の役割を果たし、電極導体１３（表層配線導体１２）の接合強度も確保される。
【００２２】
従って、本実施形態では、厚膜抵抗体１４と電極導体１３との間に、両者の中間的な２０〜３０重量％のＰｄを含むＡｇ−Ｐｄ導体層を形成しなくても、電極導体１３から厚膜抵抗体１４へのＡｇ拡散を防止できて、電極導体１２と低温焼成セラミック基板１１との接合強度を確保できるので、印刷工程が増加せず、しかも、中間層を形成する専用のＡｇ−Ｐｄ導体ペーストが不要となり、コストアップせずに済む。しかも、電極導体１３（表層配線導体１２）のガラス含有量を多くしなくても、電極導体１２と低温焼成セラミック基板１１との接合強度を確保できるので、電極導体１３（表層配線導体１２）の導通抵抗値が大きくならずに済み、回路の電気的特性が悪化せずに済む。これにより、回路の信頼性向上、コスト低減、電気的特性向上の要求を全て満たすことができる。
【００２３】
【実施例】
本発明者は、電極導体１３のＰｄ含有量、厚膜抵抗体１４のＰｄ含有量、厚膜抵抗体１４の低温焼成セラミック材料添加量の適正範囲を評価する試験を行ったので、その試験結果を次の表１に示す。
【００２４】
【表１】

Figure 0004711158
【００２５】
この試験で用いた低温焼成セラミック材料は、ＣａＯ−ＳｉＯ2 −Ａｌ2 Ｏ3 −Ｂ2 Ｏ3 系ガラス粉末：６０重量％とＡｌ2 Ｏ3 粉末：４０重量％との混合物であり、表１の各サンプル＃１〜＃１８は、焼成後の低温焼成セラミック基板１１に後付けで電極導体１３と厚膜抵抗体１４を印刷・焼成したものである。この試験では、各サンプル＃１〜＃１８を液体窒素に浸して極低温に冷却した後に、各サンプル＃１〜＃１８を液体窒素から取り出して抵抗値変化率を測定する液体窒素ディップテストを行い、抵抗値変化率が１％以下のものを合格（○）とし、抵抗値変化率が１％より大きいものを不合格（×）とした。
【００２６】
従来のように、焼成時に電極導体１３中のＡｇ原子が厚膜抵抗体１４中に拡散して、電極導体１３の内部がポーラス化（多孔質化）すると、電極導体１３と低温焼成セラミック基板１１との間の接合強度が弱くなって、液体窒素ディップテストで電極導体１３と低温焼成セラミック基板１１との接合部にクラックや剥離が発生しやすくなり、その結果、抵抗値変化率が１％より大きくなる。
【００２７】
表１の各サンプル＃１〜＃１８は、電極導体１３のＰｄ含有量が０重量％、５重量％、１０重量％のいずれかであり、厚膜抵抗体１４の全導体の合計含有量に対するＰｄ含有量が４０重量％、５０重量％、５５重量％、６０重量％のいずれかである。電極導体１３のＰｄ含有量が１０重量％より多くなると、電極導体１３の導通抵抗値が大きくなり過ぎて、回路の電気的特性が悪くなったり、半田付け性が悪化する。また、厚膜抵抗体１４は、ＡｇとＰｄの配合比が、Ａｇ：Ｐｄ＝５０：５０の付近で抵抗温度係数が最も小さくなることから、Ｐｄ含有量が４０〜６０重量％の範囲では、厚膜抵抗体１４の抵抗温度係数が最小値付近の値となり、温度変化の影響を受けにくい安定した抵抗特性が得られる。
【００２８】
実施例のサンプル＃１〜＃１２は、厚膜抵抗体１４の低温焼成セラミック材料添加量が５重量％、１０重量％、１５重量％のいずれかであり、比較例のサンプル＃１３〜＃１８は、厚膜抵抗体１４の低温焼成セラミック材料添加量が０重量％又は３重量％である。
【００２９】
この表１の試験結果から明らかなように、電極導体１３のＰｄ含有量が１０重量％以下で、厚膜抵抗体１４のＰｄ含有量が４０〜６０重量％の範囲では、厚膜抵抗体１４の低温焼成セラミック材料添加量によって抵抗値変化率が変化し、厚膜抵抗体１４の低温焼成セラミック材料添加量が増加するに従って、抵抗値変化率が小さくなり、回路の信頼性が向上する。
【００３０】
比較例のように、低温焼成セラミック材料添加量が３重量％以下では、低温焼成セラミック材料添加量が不足して、合格（○）の判定基準である抵抗値変化率≦１％の条件を満たさず、不合格（×）となった。
【００３１】
これに対し、実施例のように、厚膜抵抗体１４の低温焼成セラミック材料添加量が５重量％以上になると、抵抗値変化率が０．６％以下となり、合格（○）の判定基準である抵抗値変化率≦１％の条件を満たした。この試験結果から、電極導体１３のＰｄ含有量が１０重量％以下で、厚膜抵抗体１４のＰｄ含有量が４０〜６０重量％の範囲では、厚膜抵抗体１４の低温焼成セラミック材料添加量を５重量％以上に設定することが適正であることが確認された。
【００３２】
尚、本発明は、厚膜抵抗体１４のＰｄ含有量が４０重量％以下又は６０重量％以上でも適用可能であり、また、厚膜抵抗体１４の低温焼成セラミック材料添加量を１５重量％以上にしても良い。
【００３３】
その他、本発明は、低温焼成セラミック回路基板の内層にＡｇ−Ｐｄ系の厚膜抵抗体を形成する場合にも適用できる等、種々変更して実施できる。
【００３４】
【発明の効果】
以上の説明から明らかなように、本発明の請求項１の低温焼成セラミック回路基板によれば、電極導体をＡｇ導体又はＰｄ含有量が１０重量％以下のＡｇ−Ｐｄ導体により形成し、厚膜抵抗体をＡｇ−Ｐｄ導体とガラスとの混合物に低温焼成セラミック基板を形成する低温焼結セラミック材料と主成分が同一の低温焼成セラミック材料を５重量％以上添加した抵抗体材料により形成したので、電極導体と厚膜抵抗体との間にＡｇ−Ｐｄの中間導体層を形成しなくても、電極導体から厚膜抵抗体へのＡｇ拡散を防止できて、電極導体のポーラス化を防止できると共に、厚膜抵抗体と低温焼成セラミック基板との熱膨張係数の差を小さくできて、両者間の熱応力を小さくすることができ、信頼性を向上させながら、コスト低減と電気的特性向上の要求も満たすことができる。
【００３５】
また、請求項２では、厚膜抵抗体の全導体の合計含有量に対するＰｄ含有量の比率を４０重量％以上にしたので、厚膜抵抗体の抵抗温度係数を最小値に近付けることができ、温度変化の影響を受けにくい安定した抵抗特性を実現することができる。
【００３６】
また、請求項３では、低温焼成セラミック材料は、ＣａＯ−ＳｉＯ2 −Ａｌ2 Ｏ3 −Ｂ2 Ｏ3 系ガラス粉末とＡｌ2 Ｏ3 粉末との混合物を用いるようにしたので、信号処理の高速化に対応した高性能のセラミック回路基板を形成できると共に、該低温焼成セラミック材料を厚膜抵抗体に５重量％以上添加しても、安定した抵抗特性を得ることができる。
【図面の簡単な説明】
【図１】本発明の一実施形態を示す低温焼成セラミック回路基板の主要部の縦断面図
【符号の説明】
１１…低温焼成セラミック基板、１２…表層配線導体、１３…電極導体、１４…厚膜抵抗体。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a low-temperature fired ceramic circuit board on which a thick film resistor mainly composed of a mixture of an Ag—Pd conductor and glass is formed.
[0002]
[Prior art]
A low-temperature fired ceramic circuit board fired at 800 to 1000 ° C. can use a low-melting-point metal such as an Ag-based conductor excellent in electrical characteristics as a wiring conductor to be fired simultaneously with the ceramic, and has a dielectric constant as compared with an alumina substrate. Is advantageous in that it can cope with high speed signal processing. When forming a thick film resistor on this low-temperature fired ceramic circuit board, a RuO 2 thick film resistor paste is often used, but in a circuit that requires stable resistance characteristics that are not easily affected by temperature changes. The resistance temperature coefficient (TCR) of the thick film resistor may be required to be within ± 100 ppm / ° C., for example.
[0003]
When a thick film resistor having a sheet resistance value of 50 to 300 mΩ / □ is formed, a RuO 2 thick film resistor cannot satisfy the above requirements, and thus a resistance composed of a mixture of an Ag—Pd conductor and glass. A thick film resistor having a small resistance temperature coefficient is formed using a body material.
[0004]
In general, the resistance temperature coefficient of the Ag-Pd conductor is smaller than that when Ag or Pd is used alone, and the resistance temperature coefficient is the smallest when the mixing ratio of Ag and Pd is in the vicinity of Ag: Pd = 50: 50. . From this characteristic, a thick film resistor having an Ag—Pd conductor as a main conductor component is often used in the vicinity of Ag: Pd = 50: 50.
[0005]
[Problems to be solved by the invention]
However, the electrode conductor (thick film wiring conductor) formed on the low-temperature fired ceramic circuit board is formed of an Ag conductor or an Ag—Pd conductor containing 10% by weight or less of Pd in order to improve electrical characteristics. There are many. When an Ag—Pd thick film resistor is printed on such an electrode conductor and fired, the Pd content of the electrode conductor and the thick film resistor is greatly different, so that the Ag atoms in the electrode conductor are Ag during firing. A phenomenon occurs in which the inside of the electrode conductor becomes porous (porous) by diffusing into the thick film resistor having a small content. As a result, there is a disadvantage that the bonding strength between the electrode conductor and the low-temperature fired ceramic substrate is weakened and the reliability is deteriorated.
[0006]
As a countermeasure, an Ag—Pd conductor layer containing 20 to 30% by weight of Pd intermediate between them is formed as an intermediate conductor layer for preventing Ag diffusion between the electrode conductor and the thick film resistor. Alternatively, a large amount of glass component is blended in the electrode conductor (thick film wiring conductor) to increase the bonding strength between the electrode conductor and the ceramic substrate.
[0007]
However, when an Ag—Pd intermediate conductor layer is formed between the electrode conductor and the thick film resistor, the number of printing steps increases and an Ag—Pd conductor containing 20 to 30 wt% Pd is newly added. It is necessary and has the disadvantage of increasing costs. Further, when the glass content of the electrode conductor (thick film wiring conductor) is increased, there is a drawback that the conduction resistance of the electrode conductor (thick film wiring conductor) increases and the electrical characteristics of the circuit deteriorate.
[0008]
The present invention has been made in view of such circumstances. Therefore, the object of the present invention is to join an electrode conductor (thick film wiring conductor) for connecting an Ag-Pd thick film resistor and a low-temperature fired ceramic substrate. An object of the present invention is to provide a low-temperature fired ceramic circuit board capable of satisfying demands for cost reduction and improvement of electrical characteristics while improving strength and ensuring reliability.
[0009]
[Means for Solving the Problems]
In order to achieve the above object, in order to achieve the above object, a low-temperature fired ceramic circuit board according to claim 1 of the present invention is joined to an electrode conductor formed on the surface of the low-temperature fired ceramic substrate and the electrode conductor. The electrode conductor is formed of an Ag conductor or an Ag-Pd conductor having a Pd content of 10% by weight or less, and the thick film resistor is formed of Ag-Pd. It is formed of a resistor material obtained by adding 5% by weight or more of a low-temperature sintered ceramic material having the same main component as the low-temperature sintered ceramic material forming the low- temperature sintered ceramic substrate to a mixture of conductor and glass.
[0010]
Thus, if a thick film resistor is formed using a resistor material to which 5% by weight or more of the same kind of low temperature fired ceramic material as that of the low temperature fired ceramic substrate is added, low temperature firing is performed from the thick film resistor to the electrode conductor side during firing. The ceramic material diffuses and an intermediate layer of low temperature fired ceramic material is formed between the thick film resistor and the electrode conductor. This intermediate layer plays the role of preventing Ag diffusion from the electrode conductor to the thick film resistor, preventing the porous inside of the electrode conductor due to Ag diffusion and preventing the reduction of the bonding strength between the electrode conductor and the low-temperature fired ceramic substrate. Is done.
[0011]
In addition, since the thick film resistor is added with 5% by weight or more of the same kind of low temperature fired ceramic material as that of the low temperature fired ceramic substrate, the difference in thermal expansion coefficient between the thick film resistor and the low temperature fired ceramic substrate is reduced. The thermal stress acting on the junction between the thick film resistor and the low-temperature fired ceramic substrate is reduced. Moreover, since the glass component that oozes out from the low-temperature fired ceramic substrate during firing to the thick film resistor side and the glass component of the thick film resistor are the same type, both the glass components are fused, and the thick film resistor and low temperature fired. Bonding strength with the ceramic substrate increases. In addition, the glass component that oozes out on the surface of the low-temperature fired ceramic substrate during firing serves as an adhesive for bonding the electrode conductor (thick film wiring conductor), and the bonding strength of the electrode conductor (thick film wiring conductor) is also ensured. .
[0012]
In this case, the Ag-Pd thick film resistor has the characteristic that the temperature coefficient of resistance is minimized when the mixing ratio of Ag and Pd is in the vicinity of Ag: Pd = 50: 50. Furthermore, the Pd content with respect to the total content of all the conductors of the thick film resistor is preferably 40% by weight or more. In this way, the resistance temperature coefficient of the thick film resistor can be brought close to the minimum value, and a stable resistance characteristic that is not easily affected by temperature changes can be realized. Even if the Pd content of the thick film resistor increases and the difference in the Pd content between the electrode conductor and the thick film resistor increases, as described above, the thick film resistor is moved from the thick film resistor to the electrode conductor side during firing. Since the low-temperature fired ceramic material diffuses to form an intermediate layer of the low-temperature fired ceramic material between the thick film resistor and the electrode conductor, Ag diffusion from the electrode conductor to the thick film resistor is caused by this intermediate layer. This prevents a decrease in bonding strength between the electrode conductor and the low-temperature fired ceramic substrate due to Ag diffusion.
[0013]
Further, as a third aspect, the low-temperature fired ceramic material may be a mixture of CaO—SiO 2 —Al 2 O 3 —B 2 O 3 glass powder and Al 2 O 3 powder. This low-temperature fired ceramic material has the features of a low dielectric constant and a low thermal expansion coefficient, and can form a high-performance ceramic circuit board corresponding to high-speed signal processing. Even if it is added by weight% or more, the temperature coefficient of resistance of the thick film resistor does not increase, and stable resistance characteristics that are hardly affected by temperature change can be obtained.
[0014]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, an embodiment of the present invention will be described with reference to FIG. The low-temperature fired ceramic substrate 11 is formed of a low-temperature fired ceramic material fired at 800 to 1000 ° C., and may be either a multilayer substrate or a single-layer substrate obtained by laminating and firing a plurality of low-temperature fired ceramic green sheets. . Examples of the low-temperature fired ceramic material for forming the low-temperature fired ceramic substrate 11 include CaO—SiO 2 —Al 2 O 3 —B 2 O 3 glass powder: 50 to 65 wt% (preferably 60 wt%) and Al 2. A mixture of O 3 powder: 50 to 35% by weight (preferably 40% by weight) may be used. In addition, for example, a mixture of MgO—SiO 2 —Al 2 O 3 —B 2 O 3 glass powder and Al 2 O 3 powder, SiO 2 —B 2 O 3 glass powder and Al 2 O 3 powder A low-temperature fired ceramic material that can be fired at 800 to 1000 ° C., such as a mixture, a mixture of PbO—SiO 2 —B 2 O 3 glass powder and Al 2 O 3 powder, or cordierite crystallized glass, may be used.
[0015]
On the front surface (or back surface) of the low-temperature fired ceramic substrate 11, the surface layer wiring conductor 12 and the electrode conductor 13 are printed and fired using a paste of an Ag conductor or an Ag—Pd conductor having a Pd content of 10 wt% or less. Yes. The surface layer wiring conductor 12 and the electrode conductor 13 may be fired simultaneously with the low temperature fired ceramic substrate 11, or the surface layer wiring conductor 12 and the electrode conductor 13 are printed and fired after the low temperature fired ceramic substrate 11 is fired. May be.
[0016]
Here, when the surface layer wiring conductor 12 and the electrode conductor 13 are formed of an Ag—Pd conductor, Pd plays a role of suppressing the migration of Ag. However, when the Pd content is more than 10% by weight, the solderability is improved. Since it deteriorates and the conduction resistance value increases, the Pd content is preferably 10% by weight or less (Ag content is 90% by weight or more).
[0017]
A thick film resistor 14 is printed and fired on the front surface (or back surface) of the low-temperature fired ceramic substrate 11 across the pair of electrode conductors 13. This thick film resistor 14 is a resistor in which 5% by weight or more of a low-temperature sintered ceramic material having the same main component as the low-temperature sintered ceramic material forming the low- temperature fired ceramic substrate 11 is added to a mixture of an Ag—Pd conductor and glass. It is formed of a material paste. Further, the thick film resistor 14 has a Pd content with respect to the total content of all conductors set to 40% by weight or more. The thick film resistor 14 has a characteristic that the temperature coefficient of resistance is minimized when the mixing ratio of Ag and Pd is in the vicinity of Ag: Pd = 50: 50. Therefore, the Pd content of the thick film resistor 14 is 40%. If it is set to ˜60% by weight, the resistance temperature coefficient of the thick film resistor 14 becomes a value close to the minimum value, and stable resistance characteristics that are not easily affected by temperature change can be obtained.
[0018]
The thick film resistor 14 may be fired at the same time as the surface layer wiring conductor 12 and the electrode conductor 13, or the thick film resistor 14 may be printed and fired after the surface layer wiring conductor 12 and the electrode conductor 13 are fired. .
[0019]
For example, when the low-temperature fired ceramic material forming the low-temperature fired ceramic substrate 11 is formed of a mixture of CaO—SiO 2 —Al 2 O 3 —B 2 O 3 glass powder and Al 2 O 3 powder. The thick film resistor 14 may be added with 5% by weight or more of a mixture of CaO—SiO 2 —Al 2 O 3 —B 2 O 3 glass powder and Al 2 O 3 powder. At this time, it is desirable to use the low-temperature fired ceramic substrate 11 and the thick film resistor 14, but the low-temperature fired ceramic substrate 11 and the thick film resistor 14 have the same composition and blend ratio. Needless to say, a low-temperature fired ceramic material having a slightly different blending ratio between the glass powder and the Al 2 O 3 powder may be used. Even if the mixing ratio of the glass powder of the low-temperature fired ceramic material and the Al 2 O 3 powder is slightly different, if the glass powder and Al 2 O 3 powder of the same composition are blended, the properties of the low-temperature fired ceramic material are almost the same. It is because it becomes the same. Further, if the glass component of the low-temperature fired ceramic material is the same in the low-temperature fired ceramic substrate 11 and the thick film resistor 14, the glass component additives and the like may be slightly different.
[0020]
In the configuration of the present embodiment described above, the low-temperature fired ceramic substrate 11 having the same main component as the low-temperature fired ceramic material forming the low- temperature fired ceramic substrate 11 is used in the structure of the present embodiment described above. Since the thick film resistor 14 is formed using the resistor material added by weight% or more, the low temperature fired ceramic material diffuses from the thick film resistor 14 to the electrode conductor 13 side during firing, and the thick film resistor 14 and the electrode conductor are diffused. 13, an intermediate layer of low-temperature fired ceramic material is formed. This intermediate layer plays a role of preventing Ag diffusion from the electrode conductor 13 to the thick film resistor 14, prevents the inside of the electrode conductor 13 from being porous due to Ag diffusion, and joins the electrode conductor 12 and the low-temperature fired ceramic substrate 11. A decrease in strength is prevented.
[0021]
In addition, the thick film resistor 14 is added with 5% by weight or more of a low temperature sintered ceramic material having the same main component as the low temperature sintered ceramic material forming the low temperature fired ceramic substrate 11. The difference in thermal expansion coefficient from the low-temperature fired ceramic substrate 11 is reduced, and the thermal stress acting on the junction between the thick film resistor 14 and the low-temperature fired ceramic substrate 11 is reduced. In addition, since the glass component oozing out from the low-temperature fired ceramic substrate 11 to the thick film resistor 14 side during firing and the glass component of the thick film resistor 14 are the same type, both glass components are fused to form a thick film resistor. The bonding strength between the body 14 and the low-temperature fired ceramic substrate 11 is increased. In addition, the glass component that has oozed out on the surface of the low-temperature fired ceramic substrate 11 during firing serves as an adhesive for bonding the electrode conductor 13 (surface wiring conductor 12), and the bonding strength of the electrode conductor 13 (surface wiring conductor 12) is also high. Secured.
[0022]
Therefore, in this embodiment, the electrode conductor 13 can be formed without forming an Ag—Pd conductor layer containing 20 to 30 wt% Pd intermediate between the thick film resistor 14 and the electrode conductor 13. Diffusion to the thick film resistor 14 can be prevented, and the bonding strength between the electrode conductor 12 and the low-temperature fired ceramic substrate 11 can be ensured, so that the printing process does not increase and the dedicated Ag for forming the intermediate layer -No need for Pd conductor paste and cost increase. In addition, since the bonding strength between the electrode conductor 12 and the low-temperature fired ceramic substrate 11 can be secured without increasing the glass content of the electrode conductor 13 (surface layer wiring conductor 12), the electrode conductor 13 (surface layer wiring conductor 12) can be secured. The conduction resistance value does not need to be increased, and the electrical characteristics of the circuit do not deteriorate. As a result, it is possible to satisfy all the requirements for improving circuit reliability, reducing costs, and improving electrical characteristics.
[0023]
【Example】
The present inventor conducted a test to evaluate the appropriate ranges of the Pd content of the electrode conductor 13, the Pd content of the thick film resistor 14, and the low-temperature fired ceramic material addition amount of the thick film resistor 14. Is shown in Table 1 below.
[0024]
[Table 1]
Figure 0004711158
[0025]
The low-temperature fired ceramic material used in this test is a mixture of CaO—SiO 2 —Al 2 O 3 —B 2 O 3 glass powder: 60% by weight and Al 2 O 3 powder: 40% by weight. Samples # 1 to # 18 are obtained by printing and firing the electrode conductor 13 and the thick film resistor 14 on the low-temperature fired ceramic substrate 11 after firing. In this test, after each sample # 1 to # 18 is immersed in liquid nitrogen and cooled to an extremely low temperature, a liquid nitrogen dip test is performed in which each sample # 1 to # 18 is taken out of liquid nitrogen and the resistance value change rate is measured. Those having a resistance value change rate of 1% or less were evaluated as pass (◯), and those having a resistance value change rate greater than 1% were determined as reject (x).
[0026]
As in the past, when the Ag atoms in the electrode conductor 13 diffuse into the thick film resistor 14 during firing and the inside of the electrode conductor 13 becomes porous (porous), the electrode conductor 13 and the low-temperature fired ceramic substrate 11 The bond strength between the electrode conductor 13 and the low-temperature fired ceramic substrate 11 is likely to be cracked or peeled off in the liquid nitrogen dip test. As a result, the rate of change in resistance value is less than 1%. growing.
[0027]
In each sample # 1 to # 18 in Table 1, the Pd content of the electrode conductor 13 is 0% by weight, 5% by weight, or 10% by weight, and is based on the total content of all the conductors of the thick film resistor 14 The Pd content is 40% by weight, 50% by weight, 55% by weight or 60% by weight. When the Pd content of the electrode conductor 13 exceeds 10% by weight, the conduction resistance value of the electrode conductor 13 becomes too large, and the electrical characteristics of the circuit are deteriorated and the solderability is deteriorated. Further, the thick film resistor 14 has a resistance temperature coefficient that is the smallest when the mixing ratio of Ag and Pd is in the vicinity of Ag: Pd = 50: 50. Therefore, when the Pd content is in the range of 40 to 60% by weight, The resistance temperature coefficient of the thick film resistor 14 becomes a value in the vicinity of the minimum value, and stable resistance characteristics that are not easily affected by temperature changes can be obtained.
[0028]
In the samples # 1 to # 12 of the example, the addition amount of the low-temperature fired ceramic material of the thick film resistor 14 is 5 wt%, 10 wt%, or 15 wt%, and the samples # 13 to # 18 of the comparative example The amount of the low-temperature fired ceramic material added to the thick film resistor 14 is 0% by weight or 3% by weight.
[0029]
As is apparent from the test results in Table 1, when the Pd content of the electrode conductor 13 is 10% by weight or less and the Pd content of the thick film resistor 14 is in the range of 40 to 60% by weight, the thick film resistor 14 The resistance value change rate changes depending on the amount of low-temperature fired ceramic material added, and as the amount of low-temperature fired ceramic material added to the thick film resistor 14 increases, the resistance value change rate decreases and the reliability of the circuit improves.
[0030]
As in the comparative example, when the low-temperature fired ceramic material addition amount is 3% by weight or less, the low-temperature fired ceramic material addition amount is insufficient and satisfies the condition of the resistance value change rate ≦ 1%, which is a pass (◯) criterion. It was rejected (x).
[0031]
On the other hand, when the amount of the low-temperature fired ceramic material added to the thick film resistor 14 is 5% by weight or more as in the example, the rate of change in resistance value is 0.6% or less. A certain resistance value change rate ≦ 1% was satisfied. From this test result, when the Pd content of the electrode conductor 13 is 10% by weight or less and the Pd content of the thick film resistor 14 is in the range of 40 to 60% by weight, the low-temperature fired ceramic material addition amount of the thick film resistor 14 It was confirmed that it was appropriate to set the amount to 5% by weight or more.
[0032]
The present invention can be applied even when the Pd content of the thick film resistor 14 is 40% by weight or less or 60% by weight or more, and the low-temperature fired ceramic material addition amount of the thick film resistor 14 is 15% by weight or more. Anyway.
[0033]
In addition, the present invention can be implemented with various modifications such as being applicable to the case where an Ag-Pd thick film resistor is formed on the inner layer of a low-temperature fired ceramic circuit board.
[0034]
【The invention's effect】
As is clear from the above description, according to the low-temperature fired ceramic circuit board of claim 1 of the present invention, the electrode conductor is formed of an Ag conductor or an Ag-Pd conductor having a Pd content of 10% by weight or less. Since the resistor is formed of a resistor material obtained by adding 5 wt% or more of a low-temperature sintered ceramic material having the same main component as the low-temperature sintered ceramic material forming the low- temperature fired ceramic substrate to the mixture of the Ag—Pd conductor and the glass, Without forming an Ag-Pd intermediate conductor layer between the electrode conductor and the thick film resistor, Ag diffusion from the electrode conductor to the thick film resistor can be prevented, and the electrode conductor can be prevented from becoming porous. The difference in thermal expansion coefficient between the thick film resistor and the low-temperature fired ceramic substrate can be reduced, the thermal stress between them can be reduced, and the reliability is improved while reducing the cost and improving the electrical characteristics. Required can also be satisfied.
[0035]
In claim 2, since the ratio of the Pd content to the total content of all the conductors of the thick film resistor is set to 40% by weight or more, the resistance temperature coefficient of the thick film resistor can be brought close to the minimum value, Stable resistance characteristics that are not easily affected by temperature changes can be realized.
[0036]
According to the third aspect of the present invention, since the low-temperature fired ceramic material is a mixture of CaO—SiO 2 —Al 2 O 3 —B 2 O 3 glass powder and Al 2 O 3 powder, high-speed signal processing is possible. In addition to forming a high-performance ceramic circuit board corresponding to the increase in the thickness, a stable resistance characteristic can be obtained even when the low-temperature fired ceramic material is added to the thick film resistor by 5% by weight or more.
[Brief description of the drawings]
FIG. 1 is a longitudinal sectional view of a main part of a low-temperature fired ceramic circuit board showing an embodiment of the present invention.
DESCRIPTION OF SYMBOLS 11 ... Low-temperature baking ceramic substrate, 12 ... Surface layer wiring conductor, 13 ... Electrode conductor, 14 ... Thick film resistor.

Claims (3)

低温焼成セラミック基板の表面に形成された電極導体と、この電極導体に接合するように形成された厚膜抵抗体とを備えた低温焼成セラミック回路基板において、前記電極導体は、Ａｇ導体又はＰｄ含有量が１０重量％以下のＡｇ−Ｐｄ導体により形成され、前記厚膜抵抗体は、Ａｇ−Ｐｄ導体とガラスとの混合物に前記低温焼成セラミック基板を形成する低温焼結セラミック材料と主成分が同一の低温焼成セラミック材料を５重量％以上添加した抵抗体材料により形成されていることを特徴とする低温焼成セラミック回路基板。In a low-temperature fired ceramic circuit board comprising an electrode conductor formed on the surface of a low-temperature fired ceramic substrate and a thick film resistor formed so as to be joined to the electrode conductor, the electrode conductor contains an Ag conductor or Pd The thick film resistor is formed of an Ag-Pd conductor having an amount of 10% by weight or less, and the main component is the same as the low-temperature sintered ceramic material forming the low- temperature fired ceramic substrate in a mixture of the Ag-Pd conductor and glass. A low-temperature fired ceramic circuit board characterized by being formed of a resistor material to which 5% by weight or more of the above-mentioned low-temperature fired ceramic material is added. 前記厚膜抵抗体は、全導体の合計含有量に対するＰｄ含有量が４０重量％以上であることを特徴とする請求項１に記載の低温焼成セラミック回路基板。 2. The low-temperature fired ceramic circuit board according to claim 1, wherein the thick film resistor has a Pd content of 40 wt% or more with respect to a total content of all conductors. 前記低温焼成セラミック材料は、ＣａＯ−ＳｉＯ２−Ａｌ２Ｏ３−Ｂ２Ｏ３系ガラス粉末とＡｌ２Ｏ３粉末との混合物からなることを特徴とする請求項１又は２に記載の低温焼成セラミック回路基板。The low-temperature co-fired ceramic material, low-temperature firing of claim 1 or 2, characterized by comprising a mixture of a CaO-SiO 2 -Al 2 O 3 -B 2 O 3 based glass powder and Al 2 O 3 powder Ceramic circuit board.
JP2001204522A 2001-07-05 2001-07-05 Low temperature fired ceramic circuit board Expired - Lifetime JP4711158B2 (en)

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JP4498835B2 (en) * 2003-07-23 2010-07-07 シャープ株式会社 Circuit board, manufacturing method thereof, and electronic device

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JPH04329691A (en) * 1991-05-01 1992-11-18 Tdk Corp Conductor paste and wiring board
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JPH06168620A (en) * 1992-11-26 1994-06-14 Kawasumi Gijutsu Kenkyusho:Kk Conductive paste composition
JPH07201222A (en) * 1993-12-28 1995-08-04 Taiyo Yuden Co Ltd Conductive paste, ceramic lamination body, and manufacture of ceramic lamination body
JPH0936508A (en) * 1995-07-13 1997-02-07 Shinko Electric Ind Co Ltd Conductive paste for ceramic circuit board and ceramic circuit board
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JPS6122685A (en) * 1984-07-04 1986-01-31 富士通株式会社 Conductive paste
JPS61260603A (en) * 1985-05-14 1986-11-18 三菱電機株式会社 Electronic component
JPH04329691A (en) * 1991-05-01 1992-11-18 Tdk Corp Conductor paste and wiring board
JPH04354101A (en) * 1991-05-30 1992-12-08 Tdk Corp Glass frit, resistor paste and wiring board
JPH06168620A (en) * 1992-11-26 1994-06-14 Kawasumi Gijutsu Kenkyusho:Kk Conductive paste composition
JPH07201222A (en) * 1993-12-28 1995-08-04 Taiyo Yuden Co Ltd Conductive paste, ceramic lamination body, and manufacture of ceramic lamination body
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